Surfactant package for well treatment and method for using same

ABSTRACT

A surfactant blend for servicing wells includes a first non-ionic surfactant having a hydrophilic-lipophilic balance of between about 10 and about 15; a second non-ionic surfactant having a hydrophilic-lipophilic balance of between about 2 and about 6; and an anionic surfactant.

BACKGROUND OF THE INVENTION

The invention relates to well servicing fluids and, more particularly,to a surfactant blend which is useful in removing oil-based mud cakesand in protecting cement slurries from oil contamination.

During the well drilling process, drilling fluids are used to create amud cake upon the well walls of the formation being drilled through, soas to control fluid loss. The drilling fluid also serves to help in theremoval of cuttings or rubble from the well through circulation to thetop of the hole, and maintains stability of the hole, in addition tofluid loss control as mentioned above.

The mud cake which is left upon the walls of the hole can present aproblem, however, during subsequent cementing of the well. The mud cakecan affect the adherence of cement upon the well walls, particularly ifthe mud cake is wetted with oil, or formed from an oil-based drillingfluid.

Drilling can be carried out using a water-based fluid. Under thesecircumstances, removal of the mud cake is relatively easy, andsubsequent slurry contamination is not a major issue. However, undercertain circumstances drilling is preferred to be carried out using anoil-based drilling fluid. Under these circumstances, cementing problemscan increase.

The presence of a mud cake which is wettable with oil, or formed from anoil-based drilling fluid, can completely prevent adherence of cement tothe walls of the well due to incompatibility existing between the cementand organic contamination. This can lead to bad cementation andexpensive cement repair, particularly if the oil-based fluidcontamination occurs near a zone of interest such as an oil producingformation or the like.

One way to remove such a mud cake involves the use of organic solvents,particularly aromatic solvents, which react with the oil-wettable mudcake and dissolve same. Unfortunately, the substitution of gasoil forfriendly oils to the environment, the use of additives which can changethe wettability in the mud solids, and therefore on the well walls, andthe formation of a highly efficient mud cake through drilling fluidadditives such as polymers make organic aromatic compound-based chemicalwashing fluids problematic. This can lead to the use of high volumes ofsuch chemical washes, and/or the need for spacers between treatments inorder to obtain sufficient removal of the mud cake.

In addition, the use of oil-based chemical wash components can furtherrequire use of a water-based fluid as a spacer between the chemical washand the subsequent cement slurry so as to avoid contaminating the slurrywith organic phase from the wash. This, of course, also leads toincreased cementation costs.

Based upon the foregoing, it is clear that the use of oil-based drillingfluid can lead to substantially higher cost compared to other types ofdrilling fluid due to increased need for chemical wash and spacermaterials, and further due to operating time spent to obtain an adequatecement slurry formation. Of course, if problems occur during the firstcementing operation, costs can be multiplied due to subsequent attemptsat cementating the well.

Based upon the foregoing, it is clear that the need exists for animproved approach toward solving problems caused by mud cake formed fromoil-based drilling fluid, and for solving other problems caused by same.

It is therefore, the primary object of the present invention to providea well servicing fluid in the form of a surfactant blend which readilyresolves the aforesaid issues.

It is a further object of the present invention to provide a method fortreating a well having oil-based drilling fluid mud cake disposedthereon.

It is a still further object of the present invention to provide amethod for cementing a well wherein the cement slurry is protected fromcontamination.

It is another object of the present invention to provide a method forforming a surfactant blend.

Other objects and advantages of the present invention will appearhereinbelow.

SUMMARY OF THE INVENTION

In accordance with the present invention, the foregoing objects andadvantages have been readily attained.

According to the invention, a surfactant blend for servicing wells isprovided, which surfactant blend comprises a first non-ionic surfactanthaving a hydrophilic-lipophilic balance of between about 10 and about15; a second non-ionic surfactant having a hydrophilic-lipophilicbalance of between about 2 and about 6; and an anionic surfactant.

In further accordance with the present invention, a method is providedfor making a surfactant blend for servicing wells, which methodcomprises the steps of providing a base fluid; mixing a first non-ionicsurfactant having an HLB of between about 10 and about 15 into the basefluid to provide a first mixture; mixing an anionic surfactant into thefirst mixture to provide a second mixture; and mixing a second non-ionicsurfactant having an HLB of between about 2 and about 6 into the secondmixture to form the surfactant blend.

In further accordance with the present invention, a method is providedfor removing an oil based fluid mud cake from a well wall, comprisingthe steps of providing a well defined by a well wall and having an oilbased mud cake on the wall; and exposing the mud cake to a surfactantblend comprising a first non-ionic surfactant having ahydrophilic-lipophilic balance of between about 10 and about 15, asecond non-ionic surfactant having a hydrophilic-lipophilic balance ofbetween about 2 and about 6, and an anionic surfactant, whereby thesurfactant blend changes wettability of solids in the mud cake and formsan emulsion with oil from the mud cake.

In still further accordance with the present invention, a method isprovided for stabilizing a cement slurry, which method comprises thesteps of providing a cement slurry; mixing the cement slurry with asurfactant blend comprising a first non-ionic surfactant having ahydrophilic-lipophilic balance of between about 10 and about 15, asecond non-ionic surfactant having a hydrophilic-lipophilic balance ofbetween about 2 and about 6, and an anionic surfactant; and positioningthe cement slurry in a location exposed to oil-based fluid whereby thesurfactant blend forms an emulsion with oil from the oil-based fluid.

BRIEF DESCRIPTION OF THE DRAWINGS

A detailed description of preferred embodiments of the present inventionfollows, with reference to the attached drawings, wherein:

FIGS. 1 and 2 show accumulated volume and mass flow over time for a mudcake and a surfactant component in accordance with the presentinvention;

FIG. 3 shows accumulated volume over time for a surfactant componentexposed to both gasoil and mineral oil;

FIGS. 4 and 5 show accumulated volume and mass flow over time for a mudcake and a surfactant blend in accordance with the present invention;

FIG. 6 shows mass flow over time for various formulations in accordancewith the present invention at different temperatures;

FIG. 7 shows mass flow over time for different formulations inaccordance with the present invention and including application ofhydrochloric acid;

FIGS. 8 and 9 show electron microscope analysis of cement matrix formedafter mixing with a surfactant blend of the present invention, and thesefigures show that the silicate phases and normal phases of cementhydration are displayed in the sample; and

FIG. 10 shows an adherence record of a tensoactive slurry in accordancewith the present invention used for removal of oil-based mud cake and,substantially simultaneous, well cementation.

DETAILED DESCRIPTION

The invention relates to a surfactant blend which can advantageously beused as a well servicing fluid, particularly as a fluid for use inremoval of a mud cake formed by an oil-based drilling fluid. Thesurfactant blend of the present invention can further advantageously beincorporated into cement slurries so as to increase resistance of thesecement slurries to degradation due to contamination from oil-basedfluids or materials.

In accordance with the present invention, the surfactant blendadvantageously includes a first non-ionic component and a secondnon-ionic component, as well as an anionic component.

The first non-ionic component is advantageously a polyglycolicether-type surfactant, preferably a synthesis alcohol and morepreferably an ester modified synthesis alcohol having the formulaR—CH₂—O(CH₂CH₂O)_(n)H, wherein n is the length of the chains in thealcohol. For the first non-ionic surfactant, it is preferred that thisnon-ionic surfactant have a hydrophilic-lipophilic balance, or HLB, ofbetween about 10 and about 15. For the first non-ionic surfactant, n, orthe length of chains, is advantageously between about 10 and about 20.

The second non-ionic surfactant is also preferably a polyglycolic ethertype surfactant, more preferably an ester modified synthesis alcoholhaving a formula as set forth above. The second non-ionic surfactantadvantageously has an HLB of between about 2 and about 6, and n, or thelength of the chains of this composition, is advantageously betweenabout 3 and about 10.

The anionic surfactant is advantageously an ammonium sulfate laurylether, preferably one having between about 3 and about 15 moles ofethylene oxide.

One particularly suitable modified synthesis alcohol for use inaccordance with the present invention is ethoxylated tridecanol. Ofcourse, other synthesis alcohols can be used as well.

The surfactant blend of the present invention can advantageously bedissolved into a base fluid such as water.

In use, and advantageously, the surfactant blend when exposed to anoil-based drilling fluid mud cake, serves to change the affinity ofparticulate matter disposed within the mud cake, for example such assolids present in the mud cake, including clay. This allows dispersionof the solids into the water. In addition, the surfactant blend forms anemulsion with oil from the mud cake, dispersing the oil as a dispersedphase through the water and allowing relatively easy removal of bothsolids and oil from the mud cake and formation wall as desired.

In accordance with the present invention, the first non-ionicsurfactant, second non-ionic surfactant and anionic surfactant areadvantageously provided in the following amounts

The surfactant blend in accordance with the present invention preferablyhas concentrations of components wherein the first non-ionic surfactantis present in an amount between about 0.1 and about 12.0 vol. %, whereinthe second non-ionic surfactant is present in an amount between about0.1 and about 4.0 vol. % and wherein the anionic surfactant is presentin an amount between about 0.1 and about 6.0 vol. %.

In further accordance with the invention, the first non-ionic surfactantand second non-ionic surfactant are advantageously provided at a ratioby volume of first surfactant to second surfactant of at least about 2:1preferably at least about 3:1.

In accordance with the present invention, it has also been found thatthe surfactant blend can advantageously be used to protect cementslurries from degradation due to exposure to organic components such asoil-based drilling fluids and mud cakes. Thus, in accordance with thepresent invention, a surfactant blend as described above canadvantageously be mixed with a typical cement slurry and the cementslurry can then be positioned in a location where it will be exposed tosuch organic components. In accordance with the present invention, andadvantageously, the surfactant blend serves to change the wettability ofany solids in this situation as well, and also serves advantageously toemulsify the organic or oil-based components so that these componentsare captured and do not adversely affect the structure or behavior ofthe cement slurry either in slurry form, during gelling, or aftersolidification.

As set forth above, one particularly troublesome problem in the priorart is the need to use oil-based solvent or washing fluid to remove themud cake, after which a spacer or water-based fluid must be flushedthrough the zone before exposing the zone to the cement slurry. Oneparticular advantage of the present invention is that the surfactantblend, when incorporated into a cement slurry, can advantageouslydispose of oil-based fluid mud cakes and fluids, through offering ofwettability of solid particles and formation of an emulsion with theoil, in a single step which includes positioning of the cement slurry ina location as desired.

In further accordance with the present invention, it has been found thatthe surfactant blend in accordance with the present invention performseven more advantageously when a salt additive such as sodium chloride isincorporated into the blend. The sodium chloride can advantageously beincorporated in an amount of between about 1 and about 25 vol. %, andthis serves to greatly speed the mud cake removal when the surfactantblend is exposed to same.

It has also been found that exposing the formation to an acid wash suchas hydrochloric acid can greatly speed removal of the mud cake from theformation, if desired. This is particularly true when the mud cakeincludes additives such as hematite and the like which may be leftbehind when the rest of the mud cake is removed.

As set forth above, the surfactant blend of the present inventioncontains three basic components. It has been found in accordance withthe present invention that these components can advantageously be mixedin a preferable order. To this end it is preferred that a startingsolution of the base liquid, preferably water, be provided. The first orhigh HLB non-ionic surfactant component is then mixed with the basefluid to form a first mixture. Following this mixture, the anionicsurfactant is mixed with the first mixture so as to provide a secondmixture. The second non-ionic surfactant, which is the low HLBcomponent, is then advantageously mixed with the second mixture toprovide the final surfactant blend. This sequence of mixing has beenfound to be important. If the non-ionic surfactants are mixed in reverseorder, problems are experienced in connection with dissolving the lowHLB non-ionic surfactant. These problems are alleviated by mixing in thepreferred order as described above.

In further accordance with the invention, and as set forth above, it isa particular advantage of the present invention to utilize thesurfactant blend of the present invention to both remove mud cakes andto protect cement slurries during positioning of same within a well.

In connection with removal of the mud cake, it is believed that thesurfactant blend of the present invention advantageously serves to alterthe wettability of particulate matter contained within the mud cake,whereby this particulate matter is dispersed throughout the surfactantblends. At the same time, the components of the surfactant blend alsoadvantageously form an emulsion with oil from the mud cake, whereby theoil is removed from the well as a dispersed phase in a surfactant blend.

Still further according to the invention, the surfactant blend canadvantageously be used to protect a cement slurry by mixing with same,and this advantageously allows for a mud-cake removal and cement slurrypositioning step to be carried out at the same time.

Based upon the foregoing, it should be clear that surfactant blend andvarious methods for making and using same have been provided whichreadily resolve the problems set forth to be solved by the object of thepresent invention.

The following examples further highlight the advantageous features ofthe present invention.

EXAMPLE 1

In this example, a surfactant component having a high HLB value was usedto remove a mud cake formed with gasoil from a test formation. Thesystem was an INTOIL® system formulated with 100% gasoil. The non-ionicsurfactant component was tridecanol having an HLB of 15. This surfactantwas tested at a pH of 2 and a pH of 12, at a temperature of 248° F., 500psi and 300 rpm for 30 minutes. This testing was carried out in a mudcake evaluation cell.

The testing shows that while the mud cake itself provides a negligibleamount of accumulated volume and mass flow over time, the high HLBsurfactant component of the present invention at low and high pH is veryeffective at removal of the mud cake, or lifting of the mud cake, asshown by the increasing accumulated volume levels of FIG. 1 and the massflow of FIG. 2.

EXAMPLE 2

In this example, a similar system was studied, that is, an ethoxylatedtridecanol system, 10%, at a pH of 2 and 12. These systems were testedusing both mud cake formed from mineral oil and mud cake from gasoil.FIG. 3 shows the results in terms of accumulated volume over time, andthe values obtained with the mineral oil are not nearly as good as thoseobtained with the gasoil. Thus, a quite different result is experiencedbetween gasoil and mineral oil.

EXAMPLE 3

Taking the results of Examples 1 and 2 into consideration, a synergisticeffect was detected with the different surfactants in a surfactantblend. A surfactant blend in accordance with the present invention andhaving composition as listed in Table 1 below was used on the samemineral oil mud cake, and FIGS. 4 and 5 show the results in terms ofaccumulated volume and mass flow in connection with same. These figures,measured at a pH of 12 and 248° F., 500 psi and 300 rpm for about 30minutes, show quite efficient and effective lifting of the mud cake inaccordance with the present invention.

EXAMPLE 4

In this example, three different wash formulations were prepared, eachof which is described in Tables 1-3 below. TABLE 1 Formulation 1 OrderAdditive Concentration (% v/v) Description 1 Water 93.97 Drinking water2 TDC EO.15 2.9 Non-ionic, HLB high 3 LSA EO.3 2.5 Anionic 4 TDC EO.60.63 Non-ionic, HLB low

TABLE 2 Chemical wash (formulation 2) Order Additive Concentration (%v/v) Description 1 50 — 2 Kerosene 45 — 3 Mineral oil 5 —

TABLE 3 Chemical wash (formulation 3) Order Additive Concentration (%v/v) Description 1 30 — 2 Kerosene 60 — 3 Xylene 9 — 4 Surfactant 1Non-ionic, HLB low

The formulation of Table 1 is a surfactant blend in accordance with thepresent invention containing the surfactant components set forth inTable 1, and formed by mixing in the sequence shown in the table.

Tables 2 and 3 show conventional or field washes, one of which is formedfrom gasoil, kerosene and mineral oil, and the other of which is formedfrom gasoil, kerosene, xylene and surfactant.

Each of these formulations was then used to remove an oil-based mud cakefrom a test vessel. Measurements were taken of the chemical removalpercentage with respect to polymer concentration present in the drillingfluid, Table 4 sets forth the results which were obtained with a cutrate of 600 rpm on a BACP drilling fluid mud cake which was densifiedwith hematite. Conditions were a temperature of 185° F. and pressure of250 psi. TABLE 4 Polymer Concentration (lb/bbl) 3 5 7 Chemical Mud cakeChemical Mud cake Chemical Mud cake Chemical wash mass (gr) Removal (%)Mass (gr) Removal (gr) Mass (gr) Removal (%) None 7.30 — 6.39 — 5.80 — 17.03 3.70 5.58 12.68 4.33 25.34 2 7.29 0.14 5.89 7.82 5.03 13.28 3 7.191.51 5.69 10.95 4.8 17.24

As shown in Table 4, formulation 1 in accordance with the presentinvention showed better results for all different polymer concentrationstested as compared to the commercial washes tested.

EXAMPLE 5

Additional formulations, specifically formulations 4, 5, 6 and 7, wereprepared in accordance with the present invention, some including as afurther ingredient a densifying agent in the from of sodium chloride.Tables 5-8 show these formulations. TABLE 5 Formulation 4 Order AdditiveConcentration (% v/v) Description 1 Water 96.985 Drinking water 2 TDCEO.15 1.45 Non-ionic, HLB high 3 LSA EO.3 1.25 Anionic 4 TDC EO.5 0.315Non-ionic, HLB low

TABLE 6 Formulation 5 Order Additive Concentration (% v/v) Description 1Water 86.985 Drinking water 2 TDC EO.15 1.45 Non-ionic, HLB high 3 LSAEO.3 1.25 Anionic 4 TDC EO.6 0.315 Non-ionic, HLB low 5 NaCl 10 —

TABLE 7 Formulation 6 Order Additive Concentration (% v(v) Description 1Water 83.97 Drinking water 2 TDC EO.15 2.9 Non-ionic, HLB high 3 LSAEO.3 2.5 Anionic 4 TDC EO.6 0.63 Non-ionic, HLB low 5 NaCl 10 —

TABLE 8 Formulation 7 Order Additive Concentration (% v/v) Description 1Water 77.94 Drinking water 2 TDC EO.15 5.8 Non-ionic, HLB high 3 LSAEO.3 5 Anionic 4 TDC EO.6 1.26 Non-ionic, HLB low 5 NaCl 10 (p/v) —

The formulations of the above examples were then used to test filtratemass flow during chemical removal of a fluid mud cake which had beendensified with hematite and with 3 pounds per barrel lb/bbl of polymer.Formulations 4 and 5 were tested at 500 psi and 248° F., andformulations 1 and 6 were tested at 250 psi and 185° F. FIG. 6 shows theresults of this testing, and shows that the addition of salt intensifiesthe cleaning or lifting of the mud cake at lower temperatures, andfurther that increasing the pressure and temperature allows removal ofthe mud cake at a lower surfactant concentration.

FIG. 7 shows mass flow over time for formulations 1, 6 and 7, andfurther shows increase of the mass flow upon application of a solutionof hydrochloric acid, in this case an 8 vol. % HCl acid solution. Thissolution was applied after use of the surfactant blend of the presentinvention. A marked increase in mass flow after application of the HClis shown. This is believed to be due to dissolution of hematite by theHCl solution, at the same time as increasing the water wettability ofthe oil-based mud cake. This is particularly advantageous in accordancewith the present invention.

EXAMPLE 6

Rheological properties of a cement slurry contaminated with a 20%oil-based mud were measured. Table 9 shows these properties. TABLE 9Evaluation results of Tensoactive Slurry Compression Density Jell timeFiltrate loss Resistance 24 Slurry Formulation (ppg) (H:Min) (ml/30 min)Hr (psi) Comments H + 0.2 FL-54 + 0.02 13.1 4:00 375 300 Reference gpsFP-6L + 8% gel + 0.05 gps R-21L + 35% S-8 CMT + 0.2 FL-54 + 13.1 4:20556 200 Reference 0.02 gps FP-6L + 8% Formulation + gel + 0.05 gpsR-21L + Surfactants 35% S-8 + 4.5 gps surfactants CMT + 0.2 FL-54 + 0.0213.1 2:40 497 200 Formulation gps FP-6L + 8% gel + Without 35% S-8 + 4.5gps Retarder surfactants CMT + 0.2 FL-54 + 0.02 13.1 5:20 367 240Formulation gps FP-6L + 8% gel + With Retarder 0.06 gps R-21L + 35%S-8 + 4.5 gps surfactants CMT + 0.2 FL-54 + 0.02 12.7 6:30 367 240Formulation gps FP-6L + 8% gel + contaminated 0.05 gps R-21L + 35% with20% of S-8 + 4.5 gps oil-based mud surfactants + 20% oil mud

In the above table, CMT is cement H; CD-33 is dispersing additive; FL-54is a filtrate control additive; FP-6L is a filtrate control additive;R-21-L is a liquid retarder; and S-8 is an additive to preventregression to the cement compression. As can be seen, the slurrycontaining the surfactant blend in accordance with the present inventionmaintains its properties even with mud contamination. In this particularexample, the surfactant was only 243.2 ppm.

EXAMPLE 7

In this example, cement matrix was formed from a cement slurry treatedin accordance with the present invention and exposed to oilcontamination, electron microscopy testing was done. FIGS. 8 and 9 showthis analysis in the form of electron microscopy. Each of these figuresshow that the cement matrix is not affected by the surfactant mixture.Specifically, silicate phases and normal phases of cement hydration areshown in these figures.

EXAMPLE 8

A cement slurry in accordance with the present invention including asurfactant blend in accordance with the present invention was tested foradherence and other properties during gelling. FIG. 10 shows the testingconditions and log results, and it is clear that the cement slurry showsgood adherence even after use of the slurry itself to remove oil-basedmud cake with subsequent well cementation. This is particularlyadvantageous in accordance with the present invention.

EXAMPLE 9

In this example, various oil-based cement slurries were prepared. Table10 shows results obtained using a commercial mud (active mud from BakerHugues, density of 16.5 lpg.) while Table 11 shows results obtainedusing INTOIL® fluid 100% oil prepared in a laboratory. TABLE 10Compression Thickening time Relation resistance at 24 113° F. (° C.)dilution hr. 100° F. 3000 PSI mud Density Slurry (32° C.) (PSI) (H:MIN)oil/water (lpg) Formulation 1100 8:20 10/90 14.2 [REF] + 436 g waterwith surfactants + 44 g oil base mud 850 7:17 20/80 14.8 [REF] + 399 gwater with surfactants + 80 g oil base mud 1300 5:10 40/60 15.2 [REF] +345 g water with surfactants + 138 g oil base mud 1400 2:54 48/52 15.4[REF] + 320 g water with surfactants + 155 g oil base mud

In Table 10, [REF] means a reference composition having 684 g cement, 2g C-252, and 2 g resin. TABLE 11 Compression resistance at 24 ThickeningTime Relation Hrs. 100° F. 113° F. (° C.) 3000 Dilution Density (32° C.)(PSI) PSI (H:MIN) O/W (lpg) Formulation 900 >8:00  10/90 13.8 44 g mud100% oil + 436 g surfactants + water + 684 CMT B + 2 g C252 + 0.44GR-6 + 0.25 g Spersenne 750 8:20 20/80 13.9 80 g mud 100% oil + 399 gsurfactants + water + 684 g CMT B + 2 g C252 + 0.44 g R-6 + 0.25 gSpersenne 500 7:10 40/60 14.1 138 g mud 100% oil + 436 g surfactants +water + 684 g CMT B + 2 g C-252 800 3:00 50/50 14.8 155 g mud 100% oil +305 g surfactants + water + 684 g CMTB + 2 g C-252 + 0.44 g R-6 + 0.25 gSpersenneAs can be seen, in both cases, the resulting system has excellentrheological properties, setting time and compression-resistance, evenwith mixtures up to 50/50 cement-mud. In these examples, the surfactantconcentration was 243.0 ppm.

This invention may be embodied in other forms or carried out in otherways without departing from the spirit or essential characteristicsthereof. The present embodiment is therefore to be considered as in allrespects illustrative and not restrictive, the scope of the inventionbeing indicated by the appended claims, and all changes which comewithin the meaning and range of equivalency are intended to be embracedtherein.

1-14. (canceled)
 15. A method for removing an oil based fluid mud cakefrom a well wall, comprising the steps of: providing a well defined by awell wall and having an oil based mud cake on the wall; and exposing themud cake to a surfactant blend comprising a first non-ionic surfactanthaving a hydrophilic-lipophilic balance of between about 10 and about15, a second non-ionic surfactant having a hydrophilic-lipophilicbalance of between about 2 and about 6, and an anionic surfactant;whereby the surfactant blend changes wettability of solids in the mudcake and forms an emulsion with oil from the mud cake.
 16. The method ofclaim 15, wherein the blend has concentrations of components as follows:first non-ionic surfactant between about 0.1 and about 12.0 vol. %,second non-ionic surfactant between about 0.1 and about 4.0 vol. %, andanionic surfactant between about 0.1 and about 6.0 vol. %.
 17. Themethod of claim 15, wherein the first non-ionic surfactant and thesecond non-ionic surfactant are present at a ratio by volume of firstnon-ionic surfactant to second non-ionic surfactant of at least about 2.18. The method of claim 17, wherein the ratio is at least about 3.19-22. (canceled)